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1.
Developing efficient non‐noble and earth‐abundant hydrogen‐evolving electrocatalysts is highly desirable for improving the energy efficiency of water splitting in base. Molybdenum disulfide (MoS2) is a promising candidate, but its catalytic activity is kinetically retarded in alkaline media due to the unfavorable water adsorption and dissociation feature. A heterogeneous electrocatalyst is reported that is constructed by selenium‐doped MoS2 (Se‐MoS2) particles on 3D interwoven cobalt diselenide (CoSe2) nanowire arrays that drives the hydrogen evolution reaction (HER) with fast reaction kinetics in base. The resultant Se‐MoS2/CoSe2 hybrid exhibits an outstanding catalytic HER performance with extremely low overpotentials of 30 and 93 mV at 10 and 100 mA cm–2 in base, respectively, which outperforms most of the inexpensive alkaline HER catalysts, and is among the best alkaline catalytic activity reported so far. Moreover, this hybrid catalyst shows exceptional catalytic performance with very low overpotentials of 84 and 95 mV at 10 mA cm–2 in acidic and neutral electrolytes, respectively, implying robust pH universality of this hybrid catalyst. This work may provide new inspirations for the development of high‐performance MoS2‐based HER electrocatalysts in unfavorable basic media for promising catalytic applications.  相似文献   

2.
Designing elaborate nanostructures and engineering defects have been promising approaches to fabricate cost‐efficient electrocatalysts toward overall water splitting. In this work, a controllable Prussian‐blue‐analogue‐sacrificed strategy followed by an annealing process to harvest defect‐rich Ni‐Fe‐doped K0.23MnO2 cubic nanoflowers (Ni‐Fe‐K0.23MnO2 CNFs‐300) as highly active bifunctional catalysts for oxygen and hydrogen evolution reactions (OER and HER) is reported. Benefiting from many merits, including unique morphology, abundant defects, and doping effect, Ni‐Fe‐K0.23MnO2 CNFs‐300 shows the best electrocatalytic performances among currently reported Mn oxide‐based electrocatalysts. This catalyst affords low overpotentials of 270 (320) mV at 10 (100) mA cm?2 for OER with a small Tafel slope of 42.3 mV dec?1, while requiring overpotentials of 116 and 243 mV to attain 10 and 100 mA cm?2 for HER respectively. Moreover, Ni‐Fe‐K0.23MnO2 CNFs‐300 applied to overall water splitting exhibits a low cell voltage of 1.62 V at 10 mA cm?2 and excellent durability, even superior to the Pt/C||IrO2 cell at large current density. Density functional theory calculations further confirm that doping Ni and Fe into the crystal lattice of δ‐MnO2 can not only reinforce the conductivity but also reduces the adsorption free‐energy barriers on the active sites during OER and HER.  相似文献   

3.
Developing low‐cost bifunctional electrocatalysts with superior activity for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is of great importance for the widespread application of the water splitting technique. In this work, using earth‐abundant transition metals (i.e., nickel, iron, and copper), 3D hierarchical nanoarchitectures, consisting of ultrathin Ni–Fe layered‐double‐hydroxide (Ni–Fe LDH) nanosheets or porous Ni–Fe oxides (NiFeOx) assembled to a metallic NiCu alloy, are delicately constructed. In alkaline solution, the as‐prepared Ni–Fe LDH@NiCu possesses outstanding OER activity, achieving a current density of 10 mA cm?2 at an overpotential of 218 mV, which is smaller than that of RuO2 catalyst (249 mV). In contrast, the resulting NiFeOx@NiCu exhibits better HER activity, yielding a current density of 10 mA cm?2 at an overpotential of 66 mV, which is slightly higher than that of Pt catalyst (53 mV) but superior to all other transition metal (hydr)oxide‐based electrocatalysts. The remarkable activity of the Ni–Fe LDH@NiCu and NiFeOx@NiCu is further demonstrated by a 1.5 V solar‐panel‐powered electrolyzer, resulting in current densities of 10 and 50 mA cm?2 at overpotentials of 293 and 506 mV, respectively. Such performance renders the as‐prepared materials as the best bifunctional electrocatalysts so far.  相似文献   

4.
Hydrogen evolution reaction (HER) has prospect to becoming clean and renewable technology for hydrogen production and Ni–Mo alloy is among the best HER catalysts in alkaline electrolytes. Here, an in situ topotactic reduction method to synthesize ultrathin 2D Ni–Mo alloy nanosheets for electrocatalytic hydrogen evolution is reported. Due to its ultrathin structure and tailored composition, the as‐synthesized Ni–Mo alloy shows an overpotential of 35 mV to reach a current density of 10 mA cm?2, along with a Tafel slope of 45 mV decade?1, demonstrating a comparable intrinsic activity to state‐of‐art commercial Pt/C catalyst. Besides, the vertically aligned assemble structure of the 2D NiMo nanosheets on conductive substrate makes the electrode “superaerophobic,” thus leading to much faster bubble releasing during HER process and therefore shows faster mass transfer behavior at high current density as compared with drop drying Pt/C catalyst on the same substrate. Such in situ topotactic conversion finds a way to design and fabricate low‐cost, earth‐abundant non‐noble metal based ultrathin 2D nanostructures for electrocatalytic issues.  相似文献   

5.
The development of earth‐abundant, low cost, and versatile electrocatalysts for producing hydrogen from water electrolysis is still challenging. Herein, based on high hydrogen evolution reaction (HER) activity of transition metal phosphides, a CoP3 nanowire decorated with copper phosphides (denoted as CuPx) nanodots structures synthesized through a simple and easily scalable precursor‐transformation strategy is reported as a highly efficient HER catalyst. By decorating with CuPx nanodots, the optimized CoP3 nanowires electrode exhibits excellent catalytic activity and long‐term durability for HER in alkaline conditions, achieving a low overpotential of 49.5 mV at a geometrical catalytic current density of 10 mA cm?2 with a small Tafel slope of 58.0 mV dec?1, while also performing quite well in neutral and acidic media. Moreover, its overall performance exceeds most of the reported state‐of‐the‐art catalysts, especially under high current density of 100 mA cm?2, demonstrating its potential as a promising versatile pH universal electrocatalyst for efficient water electrolysis. These results indicate that the incorporation of earth‐abundant stable element copper can significantly enhance catalytic activity, which widens the application range of copper and provides a new path for design and selection of HER catalysts.  相似文献   

6.
Developing highly efficient earth‐abundant nickel‐based compounds is an important step to realize hydrogen generation from water. Herein, the electronic modulation of the semiconducting NiS2 by cation doping for advanced water electrolysis is reported. Both theoretical calculations and temperature‐dependent resistivity measurements indicate the semiconductor‐to‐conductor transition of NiS2 after Cu incorporation. Further calculations also suggest the advantages of Cu dopant to cathodic water electrolysis by bringing Gibbs free energy of H adsorption at both Ni sites and S sites much closer to zero. It is noteworthy that water dissociation on Cu‐doped NiS2 (Cu‐NiS2) surface is even more favorable than those on NiS2 and Pt(111). Thus, the prepared Cu‐NiS2 shows noticeably improved performance toward alkaline hydrogen and oxygen evolution reactions (HER and OER). Specifically, it requires merely 232 mV OER overpotential to drive 10 mA cm?2; in parallel with Tafel slopes of 46 mV dec?1. Regarding HER, an onset overpotential of only 68 mV is achieved. When integrated as both electrodes for water electrolysis, Cu‐NiS2 needs only 1.64 V to drive 10 mA cm?2, surpassing the state‐of‐the‐art Ir/C–Pt/C couple (1.71 V). This work opens up an avenue to engineer low‐cost and earth‐abundant catalysts performing on par with the noble‐metal‐based one for water splitting.  相似文献   

7.
Exploring earth‐abundant bifunctional electrocatalysts with high efficiency for water electrolysis is extremely demanding and challenging. Herein, density functional theory (DFT) predictions reveal that coupling Ni with Ni3C can not only facilitate the oxygen evolution reaction (OER) kinetics, but also optimize the hydrogen adsorption and water adsorption energies. Experimentally, a facile strategy is designed to in situ fabricate Ni3C nanosheets on carbon cloth (CC), and simultaneously couple with Ni nanoparticles, resulting in the formation of an integrated heterostructure catalyst (Ni–Ni3C/CC). Benefiting from the superior intrinsic activity as well as the abundant active sites, the Ni–Ni3C/CC electrode demonstrates excellent bifunctional electrocatalytic activities toward the OER and hydrogen evolution reaction (HER), which are superior to all the documented Ni3C‐based electrocatalysts in alkaline electrolytes. Specifically, the Ni–Ni3C/CC catalyst exhibits the low overpotentials of only 299 mV at the current density of 20 mA cm?2 for the OER and 98 mV at 10 mA cm?2 for the HER in 1 m KOH. Furthermore, the bifunctional Ni–Ni3C/CC catalyst can propel water electrolysis with excellent activity and nearly 100% faradic efficiency. This work highlights an easy approach for designing and constructing advanced nickel carbide‐based catalysts with high activity based on the theoretical predictions.  相似文献   

8.
Developing efficient earth‐abundant MoS2 based hydrogen evolution reaction (HER) electrocatalysts is important but challenging due to the sluggish kinetics in alkaline media. Herein, a strategy to fabricate a high‐performance MoS2 based HER electrocatalyst by modulating interface electronic structure via metal oxides is developed. All the heterostructure catalysts present significant improvement of HER electrocatalytic activities, demonstrating a positive role of metal oxides decoration in promoting the rate‐limited water dissociation step for the HER mechanism in alkaline media. The as‐obtained MoS2/Ni2O3H catalyst exhibits a low overpotential of 84 mV at 10 mA cm?2 and small charge‐transfer resistance of 1.5 Ω in 1 m KOH solution. The current density (217 mA cm?2) at the overpotential of 200 mV is about 2 and 24 times higher than that of commercial Pt/C and bare MoS2, respectively. Additionally, these MoS2/metal oxides heterostructure catalysts show outstanding long‐term stability under a harsh chronopotentiometry test. Theoretical calculations reveal the varied sensitivity of 3d‐band in different transition oxides, in which Ni‐3d of Ni2O3H is evidently activated to achieve fast electron transfer for HER as the electron‐depletion center. Both electronic properties and energetic reaction trends confirm the high electroactivity of MoS2/Ni2O3H in the adsorption and dissociation of H2O for highly efficient HER in alkaline media.  相似文献   

9.
Exploring high‐efficiency, stable, and cost‐effective bifunctional electrocatalysts for overall water splitting is greatly desirable and challenging. Herein, a newly designed hybrid catalyst with Cr‐doped FeNi–P nanoparticles encapsulated into N‐doped carbon nanotubes (Cr‐doped FeNi–P/NCN) with unprecedented electrocatalytic activity is developed by a simple one‐step heating treatment. The as‐synthesized Cr‐doped FeNi–P/NCN with moderate Cr doping exhibits admirable oxygen evolution reaction and hydrogen evolution reaction activities with overpotentials of 240 and 190 mV to reach a current density of 10 mA cm?2 in 1 m KOH solution. When used in overall water splitting as a bifunctional catalyst, it needs only 1.50 V to give a current density of 10 mA cm?2, which is superior to its typically integrated Pt/C and RuO2 counterparts (1.54 V @ 10 mA cm?2). Density functional theory calculation confirms that Cr doping into a FeNi‐host can effectively alter the relative Gibbs adsorption energy and reduces the theoretical overpotential. Additionally, the synergetic effects between Cr‐doped FeNi–P nanoparticles and NCNs are regarded as significant contributors to accelerate charge transfer and promote electrocatalytic activity in hybrid catalysts.  相似文献   

10.
Developing cost‐effective electrocatalysts with high activity and stability for hydrogen evolution reaction (HER) plays an important role in modern hydrogen economy. Amorphous molybdenum sulfide (MoSx ) has recently emerged as one of the most promising alternatives to Pt‐based catalysts in HER, especially in acidic electrolytes. Here this study reports a simple ultrasonic spray pyrolysis method to synthesize hybrid HER catalysts composed of MoSx firmly attached on entangled carbon nanotube nanospheres (MoSx /CNTs). This synthetic process is fast, continuous, highly durable, and amenable to high‐volume production with high yields and exceptional quality. The MoSx /CNTs hybrid catalyst prepared at 300 °C exhibits a low overpotential of 168 mV at the current density of 10 mA cm?2 with a small Tafel slope of 36 mV dec?1. Electrochemical measurements and X‐ray photoelectron spectroscopy analyses reveal that the CNT network not only promotes the charge transfer in corresponding HER process but also enhances the stability of the active sites in MoSx . This work demonstrates that ultrasonic spray pyrolysis is a reliable and versatile approach for synthesizing amorphous MoSx‐based HER catalysts.  相似文献   

11.
The design of cost‐efficient earth‐abundant catalysts with superior performance for the electrochemical water splitting is highly desirable. Herein, a general strategy for fabricating superior bifunctional water splitting electrodes is reported, where cost‐efficient earth‐abundant ultrathin Ni‐based nanosheets arrays are directly grown on nickel foam (NF). The newly created Ni‐based nanosheets@NF exhibit unique features of ultrathin building block, 3D hierarchical structure, and alloy effect with the optimized Ni5Fe layered double hydroxide@NF (Ni5Fe LDH@NF) exhibiting low overpotentials of 210 and 133 mV toward both oxygen evolution reaction and hydrogen evolution reaction at 10 mA cm?2 in alkaline condition, respectively. More significantly, when applying as the bifunctional overall water splitting electrocatalyst, the Ni5Fe LDH@NF shows an appealing potential of 1.59 V at 10 mA cm?2 and also superior durability at the very high current density of 50 mA cm?2.  相似文献   

12.
Herein, the authors demonstrate a heterostructured NiFe LDH‐NS@DG10 hybrid catalyst by coupling of exfoliated Ni–Fe layered double hydroxide (LDH) nanosheet (NS) and defective graphene (DG). The catalyst has exhibited extremely high electrocatalytic activity for oxygen evolution reaction (OER) in an alkaline solution with an overpotential of 0.21 V at a current density of 10 mA cm?2, which is comparable to the current record (≈0.20 V in Fe–Co–Ni metal‐oxide‐film system) and superior to all other non‐noble metal catalysts. Also, it possesses outstanding kinetics (Tafel slope of 52 mV dec?1) for the reaction. Interestingly, the NiFe LDH‐NS@DG10 hybrid has also exhibited the high hydrogen evolution reaction (HER) performance in an alkaline solution (with an overpotential of 115 mV by 2 mg cm?2 loading at a current density of 20 mA cm?2) in contrast to barely HER activity for NiFe LDH‐NS itself. As a result, the bifunctional catalyst the authors developed can achieve a current density of 20 mA cm?2 by a voltage of only 1.5 V, which is also a record for the overall water splitting. Density functional theory calculation reveals that the synergetic effects of highly exposed 3d transition metal atoms and carbon defects are essential for the bifunctional activity for OER and HER.  相似文献   

13.
To generate hydrogen, which is a clean energy carrier, a combination of electrolysis and renewable energy sources is desirable. In particular, for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in electrolysis, it is necessary to develop nonprecious, efficient, and durable catalysts. A robust nonprecious copper–iron (CuFe) bimetallic composite is reported that can be used as a highly efficient bifunctional catalyst for overall water splitting in an alkaline medium. The catalyst exhibits outstanding OER and HER activity, and very low OER and HER overpotentials (218 and 158 mV, respectively) are necessary to attain a current density of 10 mA cm?2. When used in a two‐electrode water electrolyzer system for overall water splitting, it not only achieves high durability (even at a very high current density of 100 mA cm?2) but also reduces the potential required to split water into oxygen and hydrogen at 10 mA cm?2 to 1.64 V for 100 h of continuous operation.  相似文献   

14.
Nowadays, the state‐of‐the‐art electrocatalysts for hydrogen evolution reaction (HER) are platinum group metals. Nonetheless, Pt‐based catalysts show decreased HER activity in alkaline media compared with that in acidic media due to the sluggish dissociation process of H2O on the surface of Pt. With a cost 1/25 that of Pt, Ru demonstrates a favorable dissociation kinetics of absorbed H2O. Herein, crystalline Ru0.33Se nanoparticles are decorated onto TiO2 nanotube arrays (TNAs) to fabricate Ru0.33Se @ TNA hybrid for HER. Owing to the large‐specific surface area, Ru0.33Se nanoparticles are freely distributed and the particle aggregation is eliminated, providing more active sites. The contracted electron transport pathway rendered by TiO2 nanotubes and the synergistic effect at the interface significantly improve the charge transfer efficiency in the hybrid catalyst. Compared with Ru0.33Se nanoparticles deposited directly on the Ti foil (Ru0.33Se/Ti) or carbon cloth (Ru0.33Se/CC), Ru0.33Se @ TNA shows an enhanced catalytic activity with an overpotential of 57 mV to afford a current density of 10 mA cm?2, a Tafel slope of 50.0 mV dec?1. Furthermore, the hybrid catalyst also exhibits an outstanding catalytic stability. The strategy here opens up a new synthetic avenue to the design of highly efficient hybrid electrocatalysts for hydrogen production.  相似文献   

15.
Developing cheap, abundant, and easily available electrocatalysts to drive the hydrogen evolution reaction (HER) at small overpotentials is an urgent demand of hydrogen production from water splitting. Molybdenum disulfide (MoS2) based composites have emerged as competitive electrocatalysts for HER in recent years. Herein, nickel@nitrogen‐doped carbon@MoS2 nanosheets (Ni@NC@MoS2) hybrid sub‐microspheres are presented as HER catalyst. MoS2 nanosheets with expanded interlayer spacings are vertically grown on nickel@nitrogen‐doped carbon (Ni@NC) substrate to form Ni@NC@MoS2 hierarchical sub‐microspheres by a simple hydrothermal process. The formed Ni@NC@MoS2 composites display excellent electrocatalytic activity for HER with an onset overpotential of 18 mV, a low overpotential of 82 mV at 10 mA cm?2, a small Tafel slope of 47.5 mV dec?1, and high durability in 0.5 H2SO4 solution. The outstanding HER performance of the Ni@NC@MoS2 catalyst can be ascribed to the synergistic effect of dense catalytic sites on MoS2 nanosheets with exposed edges and expanded interlayer spacings, and the rapid electron transfer from Ni@NC substrate to MoS2 nanosheets. The excellent Ni@NC@MoS2 electrocatalyst promises potential application in practical hydrogen production, and the strategy reported here can also be extended to grow MoS2 on other nitrogen‐doped carbon encapsulated metal species for various applications.  相似文献   

16.
Complementary water splitting electrocatalysts used simultaneously in the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) can simplify water splitting systems. Herein, earth‐abundant NiMoFe (NMF) and phosphorized NiMoFeP (NMFP) are synthesized as complementary overall water splitting (OWS) catalysts. First, NMF is tested as both the HER and OER promoter, which exhibits low overpotentials of 68 (HER) and 337 mV (OER). A quaternary NMFP is then prepared by simple phosphorization of NMF, which shows a much lower OER overpotential of 286 mV. The enhanced OER activity is attributed to the unique surface/core structure of NMFP. The surface phosphate acts as a proton transport mediator and expedites the rate‐determining step. With the application of OER potential, the NMFP surface is composed of Ni(OH)2 and FeOOH, active sites for OER, but the inner core consists of Ni, Mo, and Fe metals, serving as a conductive electron pathway. OWS with NMF‐NMFP requires an applied voltage of 1.452 V to generate 10 mA cm?2, which is one of the lowest values among OWS results with transition‐metal‐based electrocatalysts. Furthermore, the catalysts are combined with tandem perovskite solar cells for photovoltaic (PV)‐electrolysis, producing a high solar‐to‐hydrogen (STH) conversion efficiency of 12.3%.  相似文献   

17.
Hydrogen production from water splitting through an efficient photoelectrochemical route requires photoinduced electron transfer from light harvesters to efficient electrocatalysts. Here, the plasmon‐enhanced photoelectrical nanocatalysts (NCs) have been successfully developed by coating a monolayer MoS2 on the Cu1.75S‐Au hetero‐nanoparticle for hydrogen evolution reaction (HER). The plasmonic NCs dramatically improve the HER, leading to 29.5‐fold increase of current under 650 nm excitation (1.0 W cm?2). These NCs generate an exceptionally high current density of 200 mA cm?2 at overpotential of 182.8 mV with a Tafel slope of 39 mV per decade and excellent stability, which is better than or comparable to the Pt‐free catalysts with carbon rod as counter electrode. The enhanced HER performance can be attributed to the significantly improved broad light absorption (400–3000 nm), more efficient charge separation and abundant active edge sites of monolayer MoS2. The studies may provide a facile strategy for the fabrication of efficient plasmon‐enhanced photoelectrical NCs for HER.  相似文献   

18.
Development of cost‐effective, active trifunctional catalysts for acidic oxygen reduction (ORR) as well as hydrogen and oxygen evolution reactions (HER and OER, respectively) is highly desirable, albeit challenging. Herein, single‐atomic Ru sites anchored onto Ti3C2Tx MXene nanosheets are first reported to serve as trifunctional electrocatalysts for simultaneously catalyzing acidic HER, OER, and ORR. A half‐wave potential of 0.80 V for ORR and small overpotentials of 290 and 70 mV for OER and HER, respectively, at 10 mA cm?2 are achieved. Hence, a low cell voltage of 1.56 V is required for the acidic overall water splitting. The maximum power density of an H2–O2 fuel cell using the as‐prepared catalyst can reach as high as 941 mW cm?2. Theoretical calculations reveal that isolated Ru–O2 sites can effectively optimize the adsorption of reactants/intermediates and lower the energy barriers for the potential‐determining steps, thereby accelerating the HER, ORR, and OER kinetics.  相似文献   

19.
Developing earth‐abundant electrocatalysts for high‐efficiency hydrogen evolution reaction (HER) has become one of the leading research frontiers in energy conversion. Here, the design and in situ growth of Ag nanodots decorated Cu2O porous nanobelts networks on Cu foam (denoted as Ag@Cu2O/CF) are carried out via a simple one‐pot solution strategy at room temperature. Serving as self‐supporting electrocatalysts, Ag@Cu2O porous nanobelts provide plentiful active sites, and the 3D hybrid foams provide fast transportation for electrolyte and short diffusion path for newly formed H2 bubbles, which result in excellent electrocatalytic HER activity and long‐term stability. Owing to the synergistic effect between Ag nanodots and Cu2O porous nanobelts and CF, the hybrid electrocatalyst exhibits a low Tafel slope of 58 mV dec?1, a small overpotential of 108 mV at 10 mA cm?2, and high durability for more than 20 h at a potential of 200 mV for HER in 1.0 mol L?1 KOH solution.  相似文献   

20.
Hydrogen evolution reaction (HER) in alkaline media urgently requires electrocatalysts concurrently possessing excellent activity, flexible free‐standing capability, and low cost. A honeycombed nanoporous/glassy sandwich structure fabricated through dealloying metallic glass (MG) is reported. This free‐standing hybrid shows outstanding HER performance with a very small overpotential of 37 mV at 10 mA cm?2 and a low Tafel slope of 30 mV dec?1 in alkaline media, outperforming commercial Pt/C. By alloying 3 at% Pt into the MG precursor, a honeycombed Pt75Ni25 solid solution nanoporous structure, with fertile active sites and large contact areas for efficient HER, is created on the dealloyed MG surface. Meanwhile, the surface compressive lattice‐strain effect is also introduced by substituting the Pt lattice sites with the smaller Ni atoms, which can effectively reduce the hydrogen adsorption energy and thus improve the hydrogen evolution. Moreover, the outstanding stability and flexibility stemming from the ductile MG matrix also make the hybrid suitable for practical electrode application. This work not only offers a reliable strategy to develop cost‐effective and flexible multicomponent catalysts with low Pt usage for efficient HER, but also sheds light on understanding the alloying effects of the catalytic process.  相似文献   

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